Process and composition for multicomponent one hundred percent solid fabric softeners

ABSTRACT

The invention relates to a method of producing a mixture of a quaternary ammonium compound, fatty acid, fatty acid ester and tertiary amine salt in situ which is a highly functional mixture that is manufactured in a single step reaction whereby quaternization is completed without the aid of solvents, especially flammable solvents. The single step reaction process eliminates separate blending of individual components. The compositions obtained can be used as fabric softeners, in modified clays, as hair treating compounds and as disinfectants.

This application is a reissue application of U.S. application Ser. No.793,216, filed Nov. 7, 1991, now U.S. Pat. No. 5,221,794, which in turnis a continuation of application Ser. No. 472,738, filed on Jan. 31,1990, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a method of producing a mixture of a quaternaryammonium compound, fatty acid, fatty acid ester and tertiary amine saltin situ which is a highly functional mixture that is manufactured in asingle step reaction whereby quaternization is completed without the aidof solvents, especially flammable solvents. The single step reactionprocess eliminates separate blending of individual components.

2. Brief Description of the Prior Art

The preparation of quaternary ammonium compounds is usually conducted instainless steel or glass-lined equipment to which a tertiary amine ischarged and a solvent. Flammable solvents such as isopropyl alcohol aregenerally used although mixtures of isopropyl alcohol and watersometimes are employed or water alone is used. Flammable solvents arealso undesirable because they are a fire hazard and special handlingprocedures are required when they are used. In many applications, thesesolvents have to be stripped from the mixture when the reaction iscompleted because the ultimate use of the product is in a solventless orsolid form.

After the reactants are loaded into the reactor they are heated to atemperature of about 50 to about 100° C. after which a quaternizingreagent is added. In some instances an exotherm is produced as a resultof the quaternizing reaction and the reactor and its contents have to becooled. The rate of addition of the quaternizing agent can also becontrolled in order to minimize or eliminate the exotherm. As notedpreviously, in some instances, the solvent, if any is employed in thequaternizing reaction is stripped from the quaternary ammonium compoundobtained since some commercial uses for the compounds are in solventlesssystems. Additionally, bulk shipments of quaternary ammonium compoundswith solvents adds to transportion costs which is another reason toremove the solvents.

The largest use for quaternary ammonium compounds is as a fabricsoftener and presently accounts for more than about three quarters ofthe total market for these material. Some fabric softeners are suppliedas a liquid dispersion of from about 3% to about 10% by weight of thequaternary ammonium compound which is adapted to be added during therinse cycle of a commercial or home laundering operation. Anothersignificant fabric softening application is the utilization ofquaternary ammonium compounds in combination with a substrate such as anonwoven fabric or a polymeric foam such as a polyurethane foam, thissubstrate so treated being added to a fabric dryer such as a clothesdryer while the fabric or clothes are still damp. The quaternaryammonium compound is formulated usually with a fatty acid ester whichpromotes the transfer of the quaternary ammonium compound from thenonwoven or porous polymeric substrate to the fabric or clothes.

Lastly, quaternary ammonium compounds are now being added to both solidand liquid laundry detergent compositions so that the quaternaryammonium compound can be incorporated as a fabric softener during thewash cycle of fabrics or clothes. The most successfully utilizedquaternary ammonium compounds in this last respect are the dimethyl(dihydrogenated tallow) ammonium chlorides or methyl sulfates. Otherquaternary ammonium compounds such as imidazolines and amidoaminequaternaries are also used in this regard.

Where the quaternary ammonium compound is used on a substrate fortransfer to fabric or clothing in a fabric or clothes dryer, it hasgenerally been the practice to separately blend the fatty acid esterinto the quaternary ammonium compound which involves the extramanufacturing steps of transportion, handling and blending of the fattyacid esters into the quaternary ammonium compounds. If these steps canbe eliminated a cost savings could be realized.

Quaternary ammonium compounds are also used to manufactureorganomodified clays which may be added to drilling muds utilized indrilling oil wells, the organomodified clay providing improvedlubrication and rheological properties of the drilling muds. Theseorganoclays are also employed as thixotropic agents in plastisols,organosols, paints and other protective coatings, grease additives,foundry additives, cosmetics, resins and printing inks. The most commonquaternary ammonium compounds employed in this regard aremethyldi(hydrogenated tallow) benzylammonium chloride,dimethyldi(hydrogenated tallow) ammonium chloride anddimethyl(hydrogenated tallow) benzylammonium chloride.

Quaternary ammonium compounds are also employed as bactericides the mostcommon of which is the quaternary ammonium compound of benzylchlorideand a dimethylalkylamine, the alkyl group having from about 12 to about16 carbon atoms as well as trimethyl alkyl ammonium chlorides where thealkyl group is a long chain alkyl such as an octadecyl group.Additionally, dimethyldicoconut-oil fatty ammonium chlorides are alsoeffective disinfectants e.g. bactericides or bacteristats, especiallyagainst anaerobic bacteria which are sulfate reducers that are found inoil wells, these bacteria causing severe corrosion problems and pluggingof formations which this type of quaternary ammonium compound canminimize or eliminate. Additionally, these quaternary ammonium compoundseffective against anaerobic bacteria are also effective in removing oilfrom sand stone formations in oil wells and provide a two-fold effect orfunctioning not only as a bactericide but also in promoting so-calledsecondary recovery of oil.

An additional use of quaternary compounds is in hair treatment becauseof the antistatic effects obtained with such compounds, as well as theincreased wetting which promotes improvements in both wet and drycombing or brushing and improves luster and feel. The most commonly usedquaternary ammonium compounds in this respect are trimethylalkylammoniumchloride, pentaethoxystearylammonium chloride,dimethylstearylbenzylammonium chloride and dimethyldialkylammoniumchlorides.

It is therefore an object to overcome these and other difficultiesencountered in the prior art.

It is also an object of the present invention to provide a method formanufacturing a mixture of quaternary ammonium compounds with a fattyester inter allia which can be used in fabric softening applications. Itis also an object of the present invention to provide such mixtures.

It is a further object of the invention to provide mixtures ofquaternary ammonium compounds with fatty acid esters, amine salts andfatty acids that can be employed in any or all of the foregoingapplications.

These and other objects have been achieved according to the presentinvention which will be further understood in view of the followingdescription and claims.

SUMMARY OF THE INVENTION

It has been found that a highly functional mixture of a quaternaryammonium compound, a fatty acid ester, an ammonium salt and a fatty acidcan be obtained in a single step reaction without the aid of solvents,especially flammable solvents to thereby produce a mixture of highlyfunctional components. The single step reaction thereby eliminates theseparate blending of such individual components as the fatty acid ester,the ammonium salt and the fatty acid with the quaternary ammoniumcompound.

The advantage of the method of the present invention is that it providesa composition that is non-flammable and it is ready to be flaked orpowdered because of its bulk form and can be used as a fabric softener,a fabric lubricant, a hair condition as well as an anti-static agentthat can be released from a substrate such as a nonwoven fabric or apolymeric foam. These mixtures can also be used in combination withsynthetic detergents or as lubricant, an emulsifier, in cosmeticpreparations hair conditioning components clay modifiers, bactericidalcompositions and as a floculant.

DETAILED DESCRIPTION

As noted, the invention relates to a method for producing a quaternaryammonium mixture that is highly functional by means of a single stepreaction as well as the various compositions that can be obtainedthereby and therewith.

In its broadest aspect the invention is directed to a method ofproducing a mixture of a quaternary ammonium compound, fatty acid, fattyacid ester and tertiary amine salt by reacting a tertiary amine,quaternizing agent and fatty acid, each in amount so that said mixturewill contain at least a quaternary ammonium compound, a fatty acid,fatty acid ester and a tertiary amine salt. The tertiary amine employedaccording to the invention has the formula:

where R, R¹ and R² can be any of the following in any combination.

(1) linear or branched chain saturated or unsaturated hydrocarbon groupshaving up to about 22 carbon atoms;

(2) a lower hydroxy alkyl group;

(3) an alkyl amido alkylene group of the formula:

where R⁴ is lower alkylene and R³ is any of R, R¹ or R²;

(4) lower alkoxy group;

(5) poly(oxyloweralkylene) group; so that at least one of R, R¹ or R² isone of said linear or branched chain aliphatic saturated or unsaturatedhydrocarbon groups;

or said tertiary amine is an imidazoline of the formula:

where R⁵ is a linear or branched chain, aliphatic saturated orunsaturated hydrocarbon group having up to about 22 carbon atoms and R⁶is a lower alkylene group;

said quaternizing agent being known in the art and which will produce aquaternary ammonium compound having an anion A⁻. Generally thesequaternizing agents are those having the formula R⁷ _((a−b))X_(;)

where R⁷ is a lower alkyl group or cyclo lower alkyl group such asbenzyl, cyclohexylmethyl, tolyl, xylyl, naphthylmethyl, and X may be achlorine, iodine, bromine, sulfate, methyl sulfate, carbonate,phosphate, borate group, formate, acetate, propionate, adipate, benzoateand the like where (a) is equal to the valence of X and (b) is from 1 tothe valence of X.

said fatty acid is a linear or branched chain aliphatic saturated orunsaturated fatty acid having from about 12 to about 22 carbon atomsbased on coconut oil, vegetable oils, seed oils animal fats and fishoils;

Various tertiary amines that can be employed in this regard includedimethylamino propyl amine, amino ethylanolamine, distearly methylamine, dihydrogenated tallow methyl amine, ditallow methyl amine,dimethyl hydrogenated tallow amine, dimethyl coco amine, distearylethoxyethyl amine, stearyl bis-hydroxyethyl amine, stearyl bis(polyethoxy ethanol) amine, bis (tallowamidoethyl) 2-hydroxyethyl amine,bis (tallowamidoethyl) 2-hydroxylpropyl amine, 1-hydrogenated tallowamido ethyl -2-hydrogenated tallow imidazoline 1-ethylene bis (2tallow,1-methyl, imidazolinium) dimethyl amino propyl tallow amidoamine andhydrogenated tallow hydroxyethyl imidazoline

where R⁹, R¹⁰, R¹¹ and R¹² are subsequently defined.

The prior art also disclosed other amines that may be used such as thosedescribed in the U.S. Patents to Marschner, U.S. Pat. No. 4,859,456;Caswell et al., U.S. Pat. No. 4,857,213; Demangeon, U.S. Pat. No.4,851,141 and Mermelstein et al., U.S. Pat. No. 4,844,824 all of whichare incorporated by reference (also referred to hereafter as “the priorart cited herein.”)

Imidazoline compounds that may be used are also described in Demangeon(supra), whereas the quarternizing agents include;

dimethyl sulfate,

diethyl sulfate,

methyl chloride,

methyl bromide and

benzyl chloride as well as those cited in the prior art cited herein.

The quaternary ammonium compound thus obtained has the formula:

where R, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have been defined above;

where A⁻ is an anion based on R⁷ _((a−b))X or equivalent anions known inthe quaternary ammonium compound art;

where R⁹ is about C8 to C30, preferably about C12 to about C18 alkyl orakenyls alkenyl

R¹⁰ and R¹¹ are independently hydrogen or C1 to about C4 alkyl R¹² is C1to about C4 alkyl

m is about 2 to about 3

A⁻ is preferably an anion such as chloride, bromide, sulfate,methosulfate, nitrite, phosphate and carbosylate (i.e., acetate,adipate, propionate, benzoate)

where R⁹, R¹⁰, R¹², m and A⁻ have been previously defined.

The tertiary amine salt has the formula:

and the fatty acid ester has the formula:

wherein R⁸ is a linear or a branched chain aliphatic saturated orunsaturated hydrocarbon group having from about 11 to about 21 carbonatoms.

As used throughout this specification the terms lower alkoxy, loweralkylene and lower alkyl are intended to include compounds having up toabout 3 or about 4 carbon atoms including the various isomericconfigurations thereof e.g. t-butyl, i-butyl, i-propyl and the like andthe various mixtures thereof whether such mixtures of such groupscontain components having one, or two, or three or four carbon atoms ormore and also where such groups individually or in combination are inany of their isomeric forms.

In another embodiment, according to the method of the invention thetertiary amine, quaternizing agent and fatty acid are reacted with oneanother each in an amount so that the mixture obtained contains fromabout 10 weight percent to about 80 weight percent and especially fromabout 35 weight percent to about 55 weight percent of said quaternaryammonium compound, about 15 weight percent to about 70 weight percentand especially from about 10 weight percent to about 30 weight percentof said salt, about 1 weight percent to about 70 weight percent andespecially from about 5 weight percent to about 25 weight percent ofsaid ester and from about 5 weight percent to about 70 weight percentand especially from about 15 weight percent to about 35 weight percentof said fatty acid wherein the ratio of said quaternary ammoniumcompound to said salt is from about 2:1 to about 1:2.

In one embodiment, the method of the invention is preferably practicedso that the quaternary ammonium compound that is obtained has thestructural formula (I) wherein at least one of R, R¹ and R² is abranched chain or linear aliphatic saturated or unsaturated hydrocarbongroup having from about 12 to about 22 carbon atoms, preferablysaturated, and especially those based on hard tallow acids (i.e.hydrogenated tallow fatty acids) and the balance, if any of theaforesaid R, R¹ and R² groups is a lower alkyl group and R⁷ is a loweralkyl group. In another embodiment X is a sulfate group.

The invention also relates to a mixture of the various quaternaryammonium compounds as described above in combination with the variousfatty acid esters, fatty acids, and tertiary amine salts also asdescribed previously and in the amounts and ratios as describedpreviously.

The invention also relates to a fabric softening article of manufacturecomprising a fabric softening amount of any of the mixtures as describedherein operatively associated with a substrate that will release suchmixture to a fabric under fabric softening conditions encountered in afabric or clothes dryer and includes the use of any of the aforesaidmixtures in a fabric softening relationship with a nonwoven or wovenfiber or a polymeric open-celled or substantially open-celled foamsubstrate, such combination being prepared in a manner well known in theart. The mixture is employed in an amount from about 0.1 to about 10 gmsand especially 1 to about 39 grms per 9 in. by 11 in. sheet.

The various polymeric foams that are employed in this respect comprisepolyurethane foams as well as any of the art known equivalent foams.

Additionally, the invention is directed to a fabric cleaning compositioncomprising a detergent in combination with a fabric softening amount ofany of the mixtures described herein. These detergents can be any of theart known anionic, cationic, nonionic or amphoteric synthetic detergentsor wetting agents that are well known in the art or a soap i.e. thereaction product of a fatty acid with a alkaline hydroxide that is watersoluble e.g. fatty acid reaction products of sodium, potassium orammonium hydroxides or amines or the art known equivalents thereof.

These surfactants are further described in Kirk-Othmer, Encyclopedia ofChemical Technology, 3rd Edition Vol. 22 pp. 332-432 which isincorporated herein by reference. Some specific detergents that areespecially suitable in this regard include:

Detergents that can be employed in this respect comprise

alkyl benzene sulfate,

sodium lauryl ether sulfate

nonyl phenyl ethoxylates and

alkyl alcohol ethoxylates as well as those noted in the prior artcited.herein.

The mixture of the invention is incorporated into the detergents(whether solid or liquid) by blending in a manner well known in the art.The amount of the mixture employed is any where from about 1 to about 50and especially from about 2 to about 30 wt. % based on the quaternaryammonium compound and the active components of the detergent i.e. thecomponent of the detergent that has both organophilic and hydrophilicgroups.

The following example is illustrative.

The method of the invention as well as a mixture obtained according tothis method is examplified by the preparation of a mixture employing thefollowing components in the indicated amounts.

Components M.W. Moles % by Wt. Dihydrogenated Tallow- 523 1.00 56.63Methyl-Amine Stearic Acid 30.00 Dimethyl Sulfate 126 0.98 13.37

The amine was charged to a clean, dry reactor which was heated to 140°F. A slight nitrogen purge was employed over the amine that was chargedto prevent it from coming into contact with any air that might enterinto the reactor during the reaction. The stearic acid was then charged,mixed and heated to 140° F. after which the dimethyl sulfate was chargedin increments sufficient to maintain the temperature of the reactionmixture at 140-170° F. The reaction is exothermic and the end point ofthe reaction is indicated to some degree when an exotherm is no longerobtained. When the reaction was completed, the resultant mixture wasallowed to cool. The foregoing method produced a reaction mixture whichwas analyzed by NMR analysis showing that the mixture obtained had thefollowing components:

% Quaternary Ammonium compound 46 Fatty Acid 22 Tertiary Amine and AmineSalt 19 Methyl Ester 13

Although the invention has been described by reference to someembodiments, it is not intended that the novel method or the mixtureobtained thereby as well as the fabric softening article of manufactureand the detergent containing a fabric softening amount of the mixture belimited thereby but that certain embodiments are intended being includedas falling within the broad scope and spirit of the foregoing disclosureand the following claims.

We claim:
 1. A method of producing a mixture of quaternary ammoniumcompound, fatty acid, fatty acid ester, and tertiary amine salt byreacting in a solvent free system, a tertiary amine, quaternizing agent,and fatty acid each in an amount so that said mixture will contain atleast a quaternary ammonium compound, fatty acid, fatty acid ester andtertiary amine salt, wherein said tertiary amine has the formula:

wherein R, R¹ or R² are: (1) a linear or branched chain aliphaticsaturated or unsaturated hydrocarbon group having up to about 22 carbonatoms; (2) a hydroxy lower alkyl group; (3) an alkyl amide alkylenegroup of the formula;

where R⁴ is lower alkylene and wherein R³ is (1), (2), (4) or (5); (4) alower alkoxy group; (5) a poly(oxyloweralkylene) group; so that at leastone of R, R¹ and R² is one of said hydrocarbon groups or one of saidhydroxy lower alkyl groups; or said tertiary amine is an imidazoline ofthe formula;

wherein R⁵ is a linear or branched chain aliphatic saturated orunsaturated hydrocarbon group having up to about 22 carbon atoms and R⁶is a lower alkylene group, said quaternizing agent being is capable ofproducing a quaternary ammonium compound having anions A⁻; said fattyacid is a linear or branched chain saturated or unsaturated fatty acidhaving from about 12 to about 22 carbon atoms; said quaternary ammoniumcompound having has the formula:

wherein R⁷ is a lower alkyl group or cyclo lower alkyl group; andor thesalts of (I) and (II) wherein R— is hydrogen; said tertiary amine salthas the formula;

said fatty acid ester having has the formula:

wherein R⁸ is a linear or branched chain, aliphatic saturated orunsaturated hydrocarbon group having from about 11 to about 21 carbonatoms; and where said tertiary amine, quaternizing agent and fatty acidare reacted with one another in an amount so that said mixture obtainedcontains about 10 wt. % to about 80 wt. % of said quaternary ammoniumcompound, about 15 wt. % to about 70 wt. % of said tertiary amine salt,about 1 wt. % to about 70 wt. % of said ester and about 5 wt. % to about70 wt. % of said fatty acid whereinand the ratio of said quaternaryammonium compound to said tertiary amine salt is from about 2:1 to about1:2 on a weight basis.
 2. The A method of claim 1 where said producing amixture of quaternary ammonium compound, fatty acid, fatty acid ester,and tertiary amine salt by reacting in a solvent free system, a tertiaryamine, quaternizing agent, and fatty acid each in an amount so that saidmixture will contain at least a quaternary ammonium compound, fattyacid, fatty acid ester and tertiary amine salt, wherein said tertiaryamine is an imidazoline having the formula:

or is an amine of the formula:

where R⁹ is alkyl or alkenyl having about 8 to about 30 carbon atoms;R¹⁰ and R ¹¹ are independently hydrogen or alkyl having up to about 4carbon atoms; and R¹² is alkyl having up to about 4 carbon atoms, saidquaternizing agent is capable of producing a quaternary ammoniumcompound having anions A ⁻ ; said fatty acid is a linear or branchedchain saturated or unsaturated fatty acid having from about 12 to about22 carbon atoms; and said quaternary ammonium compound has the formula:

where R⁹ is alkyl or akenyls having about 8 to about 30 carbon atoms;R¹⁰ and R¹¹ are independently hydrogen or alkyl having up to about 4carbon atoms; R¹² is alkyl having up to about 4 carbon atoms; and thesalts of (III) or (IV) where R¹² on the nitrogen atom is hydrogen andsaid tertiary amine salt has the formula:

and wherein said tertiary amine, quaternizing agent and fatty acid arereacted with one another in an amount so that said mixture obtainedcontains about 10 wt. % to about 80 wt. % of said quaternary ammoniumcompound, about 15 wt. % to about 70 wt. % of said tertiary amine salt,about 1 wt. % to about 70 wt. % of said ester and about 5 wt. % to about70 wt. % of said fatty acid and the ratio of said quaternary ammoniumcompound to said tertiary amine salt is from about 2:1 to about 1:2 on aweight basis.
 3. The method of any of claims 1 or 2 where said tertiaryamine, quaternizing agent and fatty acid are reacted with one another inan amount so that said mixture obtained contains about 35 wt. % to about55 wt. % of said quaternary ammonium compound, about 10 wt. % to about30 wt. % of said tertiary amine salt, about 5 wt. % to about 25 wt. % ofsaid ester and about 15 wt. % to about 35 wt. % of said fatty acidwherein the ratio of said quaternary ammonium compound to said salt isfrom about 2:1 to about 1:2 on a weight basis .
 4. The method of claim 1where said quaternary ammonium compound is a compound of formula (I) orwherein at least one of the R, R¹ and R² groups is a branched chain orlinear, aliphatic saturated or unsaturated hydrocarbon group having fromabout 12 to about 22 carbon atoms and the balance, if any, of said R, R¹and R² groups is a lower alkyl group.
 5. The method of claim 4 where Ais a lower alkyl sulfate group; and where said at least one of the R, R¹and R² groups is saida saturated hydrocarbon group, it is saturated . 6.As a composition of matter, a solvent free mixture of a quaternaryammonium compound having the formula:

where R, R¹ and R² are (1) linear or branched chain aliphatic saturatedor unsaturated hydrocarbon group having up to about 22 carbon atoms; (2)a hydroxy lower alkyl group; (3) an alkyl amido alkylene group of theformula,

where R⁴ is lower alkylene and R³ is any of R, R¹ or R²; (4) a loweralkoxy group; (5) a poly(oxyloweralkylene) group; so that at least oneof R, R¹ or R² is one of said hydrocarbon groups or one of said hydroxylower alkyl groups, where R⁵ is a linear or branched chain aliphaticsaturated or unsaturated hydrocarbon group having up to about 22 carbonatoms and , R⁶ is a lower alkylene group, R⁷ is lower alkyl group orcyclo lower alkyl group, and where A⁻ is an anion; a linear or branchedchain saturated or unsaturated fatty acid having from about 12 to about22 carbon atoms; a tertiary amine salt having the formula (I) or (II)where R⁷ is hydrogen ;

and a fatty acid ester having the formula:

where R⁸ is a linear or branched chain, aliphatic saturated orunsaturated group having from about 11 to about 21 carbon atoms.
 7. TheAs a composition of claim 6 where said amine is an imidazoline havingthe formula matter, a solvent free mixture of a quaternary ammoniumcompound having the formula:

or an amine of the formula:

said quaternary ammonium compound has the formula

where R⁹ is alkyl or alkenyls having about 8 to about 30 carbon atoms;R¹⁰ and R¹¹ are independently hydrogen or alkyl having up to about 4carbon atoms; and R¹² is alkyl having up to about 4 carbon atoms; andthe salts of (III) and (IV) where R¹² on the nitrogenatom is hydrogen.A⁻ is an anion; a linear or branched chain saturated or unsaturatedfatty acid having from about 12 to about 22 carbon atoms; a tertiaryamine salt having the formula:

and a fatty acid ester having the formula:

wherein R⁷ is a lower alkyl group or cyclo lower alkyl group and R ⁸ isa linear or branched chain, aliphatic saturated or unsaturated grouphaving from about 11 to about 21 carbon atoms.
 8. The composition of anyof claims 6 or 7 where said tertiary amine, quaternizing agent and fattyacid are present in an amount of mixture contains about 10 wt. % toabout 80 wt. % of said quaternary ammonium compound, about 15 wt. % toabout 70 wt. % of said tertiary amine salt, about 1 wt. % to about 70wt. % of said ester and about 5 wt. % to about 70 wt. % of said fattyacid, and wherein the ratio of said quaternary ammonium compound to saidtertiary amine salt, is from about 2:1 to about 1:2 on a weight basis.9. The composition of any of claims 6 or 7 where said tertiary amine,quaternizing agent and fatty acid are present in an amount so that saidmixture contains about 35 wt. % to about 55 wt. % of said quaternaryammonium compound, about 10 wt. % to about 30 wt. % of said tertiaryamine salt, about 5 wt. % to about 25 wt. % of said ester and about 15wt. % to about 35 wt. % of said fatty acid wherein the ratio of saidquaternary ammonium compound to said tertiary amine salt, is from about2:1 to about 1:2 on a weight basis.
 10. The mixture of claim 6 wheresaid quaternary ammonium compound is a compound of formula (I) andwherein at least one of said R, R¹ and R² groups is a branched chain orlinear, aliphatic saturated or unsaturated hydrocarbon group having fromabout 12 to about 22 carbon atoms and the balance, if any, of said R, R¹and R² groups is a lower alkyl group.
 11. The mixture of claim 9 10whereA⁻ is a lower alkyl sulfate group and where said at least one of said R,R¹ and R² is said a saturated hydrocarbon group it is saturated .
 12. Afabric softening article of manufacture comprising a fabric softeningamount of any of the mixtures of claims 6 or 7, operatively associatedwith a substrate that will release said mixture to a fabric under fabricsoftening conditions.
 13. The article of claim 12 where said substrateis a fabric.
 14. The article of claim 12 where said substrate is aporous polymeric material.
 15. A fabric cleaning composition comprisinga detergent in combination with a fabric softening amount of themixtures of any of claims 6 or
 7. 16. The composition of claim 15 wheresaid detergent is a synthetic detergent.
 17. The composition of claim 15where said detergent is a soap.